CN110892012B - Method for producing porous body - Google Patents

Method for producing porous body Download PDF

Info

Publication number
CN110892012B
CN110892012B CN201880045284.2A CN201880045284A CN110892012B CN 110892012 B CN110892012 B CN 110892012B CN 201880045284 A CN201880045284 A CN 201880045284A CN 110892012 B CN110892012 B CN 110892012B
Authority
CN
China
Prior art keywords
urethane resin
solvent
hansen solubility
hsp
solubility parameter
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201880045284.2A
Other languages
Chinese (zh)
Other versions
CN110892012A (en
Inventor
曾雅怡
小松崎邦彦
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
DIC Corp
Original Assignee
DIC Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by DIC Corp filed Critical DIC Corp
Publication of CN110892012A publication Critical patent/CN110892012A/en
Application granted granted Critical
Publication of CN110892012B publication Critical patent/CN110892012B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
    • C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
    • C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/20—Diluents or solvents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/0838—Manufacture of polymers in the presence of non-reactive compounds
    • C08G18/0842—Manufacture of polymers in the presence of non-reactive compounds in the presence of liquid diluents
    • C08G18/0847—Manufacture of polymers in the presence of non-reactive compounds in the presence of liquid diluents in the presence of solvents for the polymers
    • C08G18/0852—Manufacture of polymers in the presence of non-reactive compounds in the presence of liquid diluents in the presence of solvents for the polymers the solvents being organic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3203—Polyhydroxy compounds
    • C08G18/3206—Polyhydroxy compounds aliphatic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6633—Compounds of group C08G18/42
    • C08G18/6637—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/664—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6666—Compounds of group C08G18/48 or C08G18/52
    • C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/6674—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/28—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a liquid phase from a macromolecular composition or article, e.g. drying of coagulum
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2101/00—Manufacture of cellular products
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2110/00—Foam properties
    • C08G2110/0033—Foam properties having integral skins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2201/00—Foams characterised by the foaming process
    • C08J2201/04—Foams characterised by the foaming process characterised by the elimination of a liquid or solid component, e.g. precipitation, leaching out, evaporation
    • C08J2201/05—Elimination by evaporation or heat degradation of a liquid phase
    • C08J2201/0502—Elimination by evaporation or heat degradation of a liquid phase the liquid phase being organic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2201/00—Foams characterised by the foaming process
    • C08J2201/04—Foams characterised by the foaming process characterised by the elimination of a liquid or solid component, e.g. precipitation, leaching out, evaporation
    • C08J2201/054—Precipitating the polymer by adding a non-solvent or a different solvent
    • C08J2201/0542—Precipitating the polymer by adding a non-solvent or a different solvent from an organic solvent-based polymer composition
    • C08J2201/0544—Precipitating the polymer by adding a non-solvent or a different solvent from an organic solvent-based polymer composition the non-solvent being aqueous
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2375/04—Polyurethanes

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Manufacturing & Machinery (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Synthetic Leather, Interior Materials Or Flexible Sheet Materials (AREA)

Abstract

A method for producing a porous body by processing a urethane resin composition containing a urethane resin (A) and a solvent (B) by a wet film-forming method, wherein the difference between the Hansen solubility parameter (B-HSP) of the solvent (B) and the Hansen solubility parameter (A-HSP) of the urethane resin (A) is 3-8 (J/cm) 3 ) 1/2 And the difference between the Hansen solubility parameter (B-HSP) of the solvent (B) and the Hansen solubility parameter (W-HSP) of water is 31.5 to 38 (J/cm) 3 ) 1/2 In (c) is used. As the solvent (B), it is preferable that the dispersion term (. Delta.D) in the Hansen solubility parameter is 15.5 to 21.0MPa 0.5 In the range of (d), the polarization term (. Delta.P) is from 7.0 to 14.5MPa 0.5 In the range of (d), the hydrogen bond term (. Delta.H) is from 4.5 to 11.0MPa 0.5 The range of (1).

Description

Method for producing porous body
Technical Field
The present invention relates to a porous body processed by a wet film-forming method.
Background
Urethane resins have both soft and tough characteristics and excellent hand feeling, and are therefore widely used for the production of artificial leathers, synthetic leathers, and the like. Particularly when used for artificial leather, synthetic leather, many intermediate layers based on urethane resins are formed to impart a hand and a bulky feeling.
The urethane resin used in the intermediate layer is usually in the form of a resin solution based on N, N-dimethylformamide (hereinafter, abbreviated as "DMF") having excellent solubility in the urethane resin, and the intermediate layer formed into a porous structure by a substitution effect between the resin solution and water can be formed by applying the urethane resin solution to a substrate and immersing the substrate in water (see, for example, patent document 1).
However, DMF has a possibility of causing allergic reaction and dermatitis, and is regarded as a high-risk substance in europe, and the specification of use in the future is put into practice. However, in this wet film formation, DMF which has excellent compatibility with urethane and water has been used as a necessary solvent, and therefore, the substitution thereof has not been advanced to a degree desired in the industry in practice.
Documents of the prior art
Patent literature
Patent document 1: japanese patent laid-open publication No. Hei 7-53764
Disclosure of Invention
Technical problem to be solved by the invention
The present invention addresses the problem of providing a method for producing a porous body by a wet film-forming method without using DMF.
Technical scheme for solving technical problem
The present invention provides a method for producing a porous body by processing a urethane resin composition containing a urethane resin (A) and a solvent (B) by a wet film-forming method, wherein the difference between the Hansen solubility parameter (B-HSP) of the solvent (B) and the Hansen solubility parameter (A-HSP) of the urethane resin (A) is 3 to 8 (J/cm) in the solvent (B) 3 ) 1/2 And the difference between the Hansen solubility parameter (B-HSP) of the solvent (B) and the Hansen solubility parameter (W-HSP) of water is 31.5 to 38 (J/cm) 3 ) 1/2 The range of (1).
Effects of the invention
According to the present invention, a porous body can be produced by a wet film-forming method without using DMF. Therefore, the present invention is particularly suitable for the production of artificial leather, i.e., synthetic leather, in which the specification for the use of DMF is becoming strict in the future. The "porous body" in the present invention refers to a material having a plurality of pores that can be obtained by itself by solidifying the urethane resin composition by a wet film-forming method, and for example, refers to a material having a long spindle-shaped or tear-drop-shaped porous structure formed in the thickness direction of the surface.
Drawings
Fig. 1 is a photograph (500 × magnification) taken with an electron microscope showing a cross-sectional view of the porous body obtained in example 1.
Detailed Description
The present invention is a method for producing a porous body by processing a urethane resin composition containing a urethane resin (a) and a solvent (B) by a wet film-forming method, provided that the solvent (B) is a specific solvent.
In the present invention, it is essential that the solvent (B) is a solvent (B) having a difference of Hansen solubility parameters (B-HSP) of the solvent (B) and Hansen solubility parameters (A-HSP) of the urethane resin (A) of 3 to 8 (J/cm) 3 ) 1/2 And the difference between the Hansen solubility parameter (B-HSP) of the solvent (B) and the Hansen solubility parameter (W-HSP) of water is 31.5 to 38 (J/cm) 3 ) 1/2 A solvent in the range of (1). In the present invention, by using the solvent (B) in the above-mentioned range, a resin solution form in which the urethane resin (a) and the solvent (B) are soluble and stable can be obtained, and a porous body can be produced by a wet film-forming method.
The hansen solubility parameter is a parameter based on the consideration that two substances having similar molecular interactions are likely to dissolve each other, and specifically, is a parameter that characterizes a solubility parameter introduced by Hildebrand (Hildebrand) in a 3-dimensional space by decomposing the solubility parameter into 3 components of a dispersion term (δ D), a polarization term (δ P), and a hydrogen bond term (δ H). The dispersion term (δ D) represents an effect by dispersion force, the polarization term (δ P) represents an effect by inter-couple force, and the hydrogen bond term (δ H) represents an effect by hydrogen bonding force.
Further, the definition and calculation of Hansen Solubility Parameters are described in Charles m.hansen, hansen Solubility Parameters; a Users Hand book (CRC Press, 2007). Further, by using the computer software "Hansen Solubility Parameters In Practice (HSPiP)", even a solvent having no parameter value described in the literature can be used to calculate the Hansen Solubility parameter from the chemical structure. In the present invention, the values of solvents having the parameter values described in the literature are used, and the values of parameters calculated by HSPiP version 4.1.06 are used for solvents having no parameter values described in the literature. The difference (absolute value) between the Hansen solubility parameter (B-HSP) of the solvent (B) and the Hansen solubility parameter (A-HSP) of the urethane resin (A), and the difference (absolute value) between the Hansen solubility parameter (B-HSP) of the solvent (B) and the Hansen solubility parameter (W-HSP) of water were also calculated in this way.
The solvent (B) may be 1 kind of solvent, or 2 or more kinds of solvents may be used in combination. When 2 or more solvents are used in combination, 3 parameters of hansen solubility parameters of the respective solvents may be weighted-averaged, and the weighted-averaged 3 parameters may be used in combination so that their values fall within the above-described range.
The solvent (B) is preferably one having a dispersion term (δ D) of 15.5 to 21MPa in the Hansen solubility parameter, from the viewpoint of forming more favorable pores 0.5 More preferably 16.0 to 20MPa 0.5 The range of (1). For the same reason, the polarization term (. Delta.P) is preferably 7 to 14.5MPa 0.5 More preferably 8 to 13.5MPa 0.5 The range of (1). Further, for the same reason, the hydrogen bond term (. Delta.H) is preferably 4.5 to 11MPa 0.5 More preferably 5 to 10MPa 0.5 The range of (1).
Specific examples of the solvent (B) include: <xnotran> N, N,2- ( :20.14, (δ D): 16.7, (δ P): 9.2, (δ H): 6.5), N, N- ( :21.81, (δ D): 17.3, (δ P): 10.6, (δ H): 8.0), N, N- ( :21.28, (δ D): 16.4, (δ P): 11.3, (δ H): 7.5), N, N- ( :22.42, (δ D): 16.8, (δ P): 11.5, (δ H): 9.4), N, N- ( :19.65, (δ D): 16.9, (δ P): 9.2, (δ H): 4.0), 1,3- -2- ( :22.29, (δ D): 18.2, (δ P): 10.0, (δ H): 8.1), N- ( :22.74, (δ D): 18.0, (δ P): 12.0, (δ H): 7.0), 2- ( :23.58, </xnotran> Dispersion term (δ D): 18.2, polarization term (δ P): 12.0, hydrogen bond term (δ H): 9.0 Etc.).
The solvent (B) is preferably N, 2-trimethylpropionamide and/or N, N-dimethylacrylamide, regardless of the type of the urethane resin (a), from the viewpoint of more stably forming a porous structure.
The content of the solvent (B) is preferably in the range of 10 to 90 mass%, more preferably in the range of 20 to 80 mass% in the urethane resin composition, from the viewpoint of solubility of the urethane resin (a).
As the urethane resin (a) used in the present invention, a reaction product of a polyol (a 1) and a polyisocyanate (a 2) can be used.
Examples of the polyol (a 1) include polyester polyols, polyether polyols, and polycarbonate polyols. These polyhydric alcohols may be used alone, or 2 or more kinds thereof may be used in combination. In the field of porous body production, polyester polyols, polyether polyols (excluding polyethylene glycols), and polycarbonate polyols are most commonly used as the polyol (a 1). Of these polyols, polyester polyols having moderate hydrophilicity are known to be most likely to produce porous bodies, and polycarbonate polyols are known to be the next most likely to be porous, while hydrophobic polyether polyols (excluding polyethylene glycols) are most likely to be porous. However, in the present invention, by using the specific solvent (B), even when any of the above polyols is used, a porous body can be easily produced by a wet film formation method.
The number average molecular weight of the polyol (a 1) is preferably in the range of 500 to 10000, more preferably 700 to 8000, from the viewpoint of mechanical properties and flexibility of the porous body. The number average molecular weight of the polyol (a 1) is a value measured by a Gel Permeation Chromatography (GPC) method.
In the polyol (a 1), a chain extender (a 1-1) having a number average molecular weight of less than 500 may be used in combination as necessary. As the chain extender (a 1-1), for example, a chain extender having a hydroxyl group, a chain extender having an amino group, or the like can be used. These chain extenders (a 1-1) may be used alone or in combination of 2 or more.
Examples of the chain extender having a hydroxyl group include aliphatic polyol compounds such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, 1, 3-propanediol, 1, 3-butanediol, 1, 4-butanediol, hexanediol, sucrose, methylene glycol, glycerol, and sorbitol; aromatic polyol compounds such as bisphenol A, 4' -dihydroxybiphenyl, 4' -dihydroxydiphenyl ether, 4' -dihydroxydiphenyl sulfone, hydrogenated bisphenol A, and hydroquinone; water, and the like. These chain extenders may be used alone, or 2 or more kinds may be used in combination.
Examples of the chain extender having an amino group include ethylenediamine, 1, 2-propylenediamine, 1, 6-hexamethylenediamine, piperazine, 2-methylpiperazine, 2, 5-dimethylpiperazine, isophoronediamine, 4' -dicyclohexylmethanediamine, 3' -dimethyl-4, 4' -dicyclohexylmethanediamine, 1, 2-cyclohexanediamine, 1, 4-cyclohexanediamine, aminoethylethanolamine, hydrazine, diethylenetriamine, triethylenetetramine, and the like. These chain extenders may be used alone, or 2 or more kinds may be used in combination.
Examples of the polyisocyanate (a 2) include aromatic polyisocyanates such as 4,4 '-diphenylmethane diisocyanate, 2,4' -diphenylmethane diisocyanate, carbodiimide-modified diphenylmethane diisocyanate, crude diphenylmethane diisocyanate, phenylene diisocyanate, toluene diisocyanate, naphthalene diisocyanate, xylene diisocyanate, and tetramethylxylene diisocyanate; aliphatic polyisocyanates such as hexamethylene diisocyanate and lysine diisocyanate; and alicyclic polyisocyanates such as cyclohexane diisocyanate, hydrogenated xylene diisocyanate, isophorone diisocyanate, and dicyclohexylmethane diisocyanate. These polyisocyanates may be used alone or in combination of 2 or more.
Examples of the method for producing the urethane resin (a) include: a method in which the polyol (a 1), the polyisocyanate (a 2) and, if necessary, the chain extender (a 1-1) are added and reacted. These reactions are preferably carried out at a temperature of 50 to 100 ℃ for approximately 3 to 10 hours. The reaction may be carried out in the solvent (B) described later.
The molar ratio of the total of the hydroxyl groups of the polyol (a 1) and the hydroxyl groups and amino groups of the chain extender (a 1-1) to the isocyanate groups of the polyisocyanate (a 2) is preferably in the range of 0.8 to 1.2, more preferably in the range of 0.9 to 1.1 in terms of [ (isocyanate groups)/(hydroxyl groups and amino groups) ].
The weight average molecular weight of the urethane resin (a) obtained by the above method is preferably in the range of 5000 to 500000, more preferably in the range of 10000 to 300000, and further preferably in the range of 30000 to 150000, from the viewpoint of mechanical strength and flexibility of the porous body. The weight average molecular weight of the urethane resin (a) is a value measured in the same manner as the number average molecular weight of the polyol (a 1).
The urethane resin composition contains the urethane resin (a) and the solvent (B) as essential components, but may contain other additives as needed.
Examples of the other additives include pigments, flame retardants, plasticizers, softening agents, stabilizers, waxes, antifoaming agents, dispersants, penetrants, surfactants, fillers, mildewproofing agents, antibacterial agents, ultraviolet absorbers, antioxidants, weather-resistant stabilizers, optical brighteners, anti-aging agents, and tackifiers. These additives may be used alone or in combination of 2 or more.
Next, a method for producing a porous body from the urethane resin composition by a wet film formation method will be described.
The wet film-forming method is a method of producing a porous body by applying or impregnating the urethane resin composition to the surface of a base material, and then bringing water, water vapor, or the like into contact with the applied surface or the impregnated surface to solidify the urethane resin (a).
As the substrate to which the urethane resin composition is applied, for example, a substrate composed of a nonwoven fabric, a woven fabric, or a knitted fabric; resin films, and the like. As materials constituting the base material, for example, chemical fibers such as polyester fibers, nylon fibers, acrylic fibers, polyurethane fibers, acetate fibers, rayon fibers, polylactic acid fibers, and the like; cotton, hemp, silk, wool, a blend fiber thereof, and the like.
The surface of the base material may be subjected to antistatic treatment, mold release treatment, hydrophobic treatment, water-absorbing treatment, antibacterial/deodorant treatment, antibacterial treatment, ultraviolet-shielding treatment, or the like as required.
Examples of the method for coating or impregnating the surface of the base material with the urethane resin composition include a gravure coating method, a blade coating method, a tube coating method, and a comma coating method. In this case, the amount of the organic solvent (B) used may be adjusted as necessary in order to adjust the viscosity of the urethane resin composition and improve the coating workability.
The thickness of the coating film containing the urethane resin composition applied or impregnated by the above method is preferably in the range of 0.5 to 5mm, and more preferably in the range of 0.5 to 3 mm.
Examples of the method of bringing water or water vapor into contact with the coated surface formed by coating or impregnating the urethane resin composition include: a method of immersing a substrate provided with a coating layer and an impregnation layer comprising the urethane resin composition in a water bath; and a method of spraying water onto the coated surface using a sprayer or the like. The immersion is preferably carried out in a water bath at 5 to 60 ℃ for about 2 to 20 minutes.
The porous body obtained by the above method is preferably subjected to extraction and removal of the solvent (B) by washing the surface thereof with water or warm water at normal temperature, followed by drying. The washing is preferably carried out in water at 5 to 60 ℃ for about 20 to 120 minutes, and the water used for washing is preferably replaced 1 or more times or continuously replaced with running water. Preferably, the drying is performed for about 10 to 60 minutes using a dryer or the like adjusted to 80 to 120 ℃.
As described above, according to the present invention, a porous body obtained by a wet film formation method can be produced without using DMF. Therefore, the present invention is particularly suitable for the production of artificial leather-synthetic leather, in which the specification for DMF will become strict in future. In addition, the present invention can be used for polishing pads; a back pad for polishing; medical and health materials such as operating gowns and sheets; building material sheets such as wind-proof and water-proof sheets and anti-dewing sheets; packaging materials for desiccants, fragrances, and the like; agricultural sheets, various spacers, and packaging.
Examples
The present invention will be described in further detail below with reference to examples.
Synthesis example 1 Synthesis of urethane resin (A-1)
100 parts by mass of polyester polyol ("CMA-244" manufactured by DIC corporation, number average molecular weight: 2000), 8 parts by mass of ethylene glycol, 250 parts by mass of N, N, 2-trimethylpropionamide, and 45 parts by mass of 4,4' -diphenylmethane diisocyanate were charged into a reaction apparatus equipped with a stirrer, a reflux vessel, and a thermometer, and reacted with stirring until the viscosity at 85 ℃ reached 600dPa · s, and then 0.22 part by mass of methanol was added thereto and reacted to obtain a urethane resin composition containing the urethane resin (A-1).
Synthesis example 2 Synthesis of urethane resin (A-2)
In a reaction apparatus equipped with a stirrer, a reflux vessel and a thermometer, 100 parts by mass of a polyester polyol ("CMA-244" manufactured by DIC corporation, number average molecular weight: 2000), 8 parts by mass of ethylene glycol, 250 parts by mass of N, N-dimethylacrylamide and 45 parts by mass of 4,4' -diphenylmethane diisocyanate were charged, and the mixture was reacted with stirring until the viscosity at 85 ℃ reached 600dPa s, and then 0.22 part by mass of methanol was added to the mixture to carry out the reaction, thereby obtaining a urethane resin composition containing a urethane resin (A-2).
[ Synthesis example 3] Synthesis of urethane resin (A-3)
100 parts by mass of polytetramethylene glycol (number average molecular weight: 2000), 8 parts by mass of ethylene glycol, 250 parts by mass of N, N, 2-trimethylpropionamide, and 45 parts by mass of 4,4' -diphenylmethane diisocyanate were charged into a reaction apparatus equipped with a stirrer, a reflux vessel, and a thermometer, and were reacted with stirring until the viscosity at 85 ℃ reached 600dPa s, and then 0.22 part by mass of methanol was added thereto and reacted, thereby obtaining a urethane resin composition containing the urethane resin (A-3).
Synthesis example 4 Synthesis of urethane resin (A-4)
100 parts by mass of polytetramethylene glycol (number average molecular weight: 2000), 8 parts by mass of ethylene glycol, 250 parts by mass of N, N-dimethylacrylamide, and 45 parts by mass of 4,4' -diphenylmethane diisocyanate were charged into a reaction apparatus equipped with a stirrer, a reflux vessel, and a thermometer, and reacted with stirring until the viscosity at 85 ℃ reached 600 dPas, and then 0.22 part by mass of methanol was added thereto and reacted to obtain a urethane resin composition containing urethane resin (A-4).
[ method for measuring number average molecular weight of polyol ]
The number average molecular weight of the polyol used in the synthesis examples is a value measured by Gel Permeation Chromatography (GPC) under the following conditions.
A measuring device: high-speed GPC apparatus (HLC-8220 GPC, manufactured by Tosoh corporation)
A chromatographic column: the following columns manufactured by Tosoh corporation were used in series.
"TSKgel G5000" (7.8mmI.D.. Times.30 cm). Times.1 roots
"TSKgel G4000" (7.8mmI.D.. Times.30 cm). Times.1 roots
"TSKgel G3000" (7.8mmI.D.. Times.30 cm). Times.1 roots
"TSKgel G2000" (7.8mmI.D.. Times.30 cm). Times.1 roots
A detector: RI (differential refractometer)
Column temperature: 40 deg.C
Eluting solvent: tetrahydrofuran (THF)
Flow rate: 1.0 mL/min
Injection amount: 100 μ L (tetrahydrofuran solution with a sample concentration of 0.4% by mass)
Standard sample: the calibration curve was prepared using the following standard polystyrene.
(Standard polystyrene)
TSKgel Standard polystyrene A-500 manufactured by Tosoh corporation "
TSKgel Standard polystyrene A-1000 manufactured by Tosoh corporation "
TSKgel Standard polystyrene A-2500, manufactured by Tosoh corporation "
TSKgel Standard polystyrene A-5000 manufactured by Tosoh corporation "
TSKgel Standard polystyrene F-1, manufactured by Tosoh corporation "
TSKgel Standard polystyrene F-2 manufactured by Tosoh corporation "
TSKgel Standard polystyrene F-4 manufactured by Tosoh corporation "
TSKgel Standard polystyrene F-10 manufactured by Tosoh corporation "
TSKgel Standard polystyrene F-20, manufactured by Tosoh corporation "
TSKgel Standard polystyrene F-40, manufactured by Tosoh corporation "
TSKgel Standard polystyrene F-80 manufactured by Tosoh corporation "
TSKgel Standard polystyrene F-128 manufactured by Tosoh corporation "
TSKgel Standard polystyrene F-288 manufactured by Tosoh corporation "
TSKgel Standard polystyrene F-550 manufactured by Tosoh corporation "
[ example 1]
100 parts by mass of the urethane resin composition obtained in Synthesis example 1 was further diluted with 30 parts by mass of N, N, 2-trimethylpropionamide, and applied to a polyethylene terephthalate (PET) film to a thickness (Wet) of 1 mm. Next, the coated substrate was immersed in a coagulation bath (water at 25 ℃) for 10 minutes to coagulate the urethane resin (a-1). Subsequently, the substrate was immersed in water at 50 ℃ for 60 minutes, and the solvent was washed. After the washing, the base material was dried with hot air at 120 ℃ for 30 minutes to obtain a porous body.
[ example 2]
100 parts by mass of the urethane resin composition obtained in Synthesis example 2 was further diluted with 30 parts by mass of N, N-dimethylacrylamide, and applied onto a polyethylene terephthalate (PET) film so as to have a thickness (Wet) of 1 mm. Next, the coated substrate was immersed in a coagulation bath (water at 25 ℃) for 10 minutes to coagulate the urethane resin (a-2). Subsequently, the substrate was immersed in water at 50 ℃ for 60 minutes, and the solvent was washed. After washing, the substrate was dried with hot air at 120 ℃ for 30 minutes to obtain a porous body.
[ example 3]
100 parts by mass of the urethane resin composition obtained in Synthesis example 3 was further diluted with 30 parts by mass of N, N, 2-trimethylpropionamide, and applied to a polyethylene terephthalate (PET) film to a thickness (Wet) of 1 mm. Next, the coated substrate was immersed in a coagulation bath (water at 25 ℃) for 10 minutes to coagulate the urethane resin (a-3). Subsequently, the substrate was immersed in water at 50 ℃ for 60 minutes, and the solvent was washed. After the washing, the base material was dried with hot air at 120 ℃ for 30 minutes to obtain a porous body.
[ example 4]
100 parts by mass of the urethane resin composition obtained in Synthesis example 4 was further diluted with 30 parts by mass of N, N-dimethylacrylamide, and applied onto a polyethylene terephthalate (PET) film so as to have a thickness (Wet) of 1 mm. Next, the coated substrate was immersed in a coagulation bath (water at 25 ℃) for 10 minutes to coagulate the urethane resin (a-4). Subsequently, the substrate was immersed in water at 50 ℃ for 60 minutes, and the solvent was washed. After the washing, the base material was dried with hot air at 120 ℃ for 30 minutes to obtain a porous body.
Comparative example 1 Synthesis of urethane resin (A' -1)
In a reaction apparatus equipped with a stirrer, a reflux vessel and a thermometer, 100 parts by mass of a polyester polyol ("CMA-244" manufactured by DIC corporation, number average molecular weight: 2000), 8 parts by mass of ethylene glycol, 250 parts by mass of gamma-butyrolactone and 45 parts by mass of 4,4' -diphenylmethane diisocyanate were charged, and the reaction was carried out at 85 ℃ with stirring, but the product was gelled in the process.
[ method of confirming porous body ]
Whether or not the porous bodies obtained in the examples were formed was confirmed by observing the porous bodies obtained in the examples using a scanning electron microscope "SU3500" (magnification 500 ×) manufactured by hitachi high-tech co. Examples of the confirmed porous bodies were evaluated as "T", and examples not confirmed were evaluated as "F".
Figure BDA0002356820340000111
The abbreviation in "Table 1" is as follows.
"DMIB": n, N, 2-trimethylpropanamides
"DMAA": n, N-dimethylacrylamide
"GBL": gamma-butyrolactone
It can also be confirmed in FIG. 1 that a porous body was obtained without using DMF in the present invention.
On the other hand, comparative example 1 is an embodiment using gamma-butyrolactone in which the difference between the hansen solubility parameter (B-HSP) of the solvent (B) and the hansen solubility parameter (a-HSP) of the urethane resin (a) is out of the range defined in the present invention, but gelation occurs, and the urethane resin (a) is insoluble, and a porous body cannot be obtained.

Claims (2)

1. A method for producing a porous body, characterized in that a urethane resin composition containing a urethane resin (A) and a solvent (B) is processed by a wet film-forming method,
the urethane resin (A) is a reaction product of a polyol (a 1) and a polyisocyanate (a 2),
the polyol (a 1) comprises 1 or more selected from the group consisting of polyester polyols, polyether polyols and polycarbonate polyols having a number average molecular weight of 500 to 10,000,
the polyisocyanate (a 2) is at least 1 selected from the group consisting of aromatic polyisocyanates, aliphatic polyisocyanates and alicyclic polyisocyanates,
as the solvent (B), there may be mentioned,
the difference between the Hansen solubility parameter B-HSP of the solvent (B) and the Hansen solubility parameter A-HSP of the urethane resin (A) is 3-8 (J/cm) 3 ) 1/2 In a range of (A) and
the difference between the Hansen solubility parameter B-HSP of the solvent (B) and the Hansen solubility parameter W-HSP of water is 31.5 to 38 (J/cm) 3 ) 1/2 In the range of (a) to (b),
the solvent (B) is N, N, 2-trimethyl propionamide and/or N, N-dimethyl acrylamide.
2. The method for producing a porous body according to claim 1, wherein the solvent (B) is N, N, 2-trimethylpropanamide or N, N-dimethylacrylamide.
CN201880045284.2A 2017-08-03 2018-06-19 Method for producing porous body Active CN110892012B (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
JP2017150680 2017-08-03
JP2017-150680 2017-08-03
PCT/JP2018/023234 WO2019026446A1 (en) 2017-08-03 2018-06-19 Porous-object production method

Publications (2)

Publication Number Publication Date
CN110892012A CN110892012A (en) 2020-03-17
CN110892012B true CN110892012B (en) 2022-10-21

Family

ID=65233700

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201880045284.2A Active CN110892012B (en) 2017-08-03 2018-06-19 Method for producing porous body

Country Status (5)

Country Link
US (1) US11111353B2 (en)
EP (1) EP3663343A4 (en)
CN (1) CN110892012B (en)
TW (1) TWI749248B (en)
WO (1) WO2019026446A1 (en)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3816064B1 (en) * 2018-07-24 2022-12-14 Kyocera Corporation Hand-held member and hand-held-type article
JP6759415B1 (en) * 2019-05-23 2020-09-23 大日精化工業株式会社 Polyurethane resin and articles
JP7484208B2 (en) * 2020-02-14 2024-05-16 Dic株式会社 Urethane resin composition and method for producing porous body

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0636474A1 (en) * 1993-07-28 1995-02-01 Shell Internationale Researchmaatschappij B.V. A process for preparing laminates, and laminates so prepared
EP0943310A1 (en) * 1998-03-09 1999-09-22 L'oreal Film-forming composition comprising aa aqueous polyurethane dispersion and a plasticizer
JP2005238597A (en) * 2004-02-25 2005-09-08 Terumo Corp Sheetlike porous body and its manufacturing method
JP4586944B1 (en) * 2009-05-25 2010-11-24 Ｄｉｃ株式会社 Porous body manufacturing method and porous body, laminate and leather-like sheet obtained thereby
CN101945949A (en) * 2008-02-25 2011-01-12 Dic株式会社 Manufacture method, porous polyurethane object and the water vapour permeability film of the solvable type polyurethane resin combination of alcohol
JP2011073112A (en) * 2009-09-30 2011-04-14 Fujibo Holdings Inc Polishing pad and method of manufacturing polishing pad
WO2016190080A1 (en) * 2015-05-25 2016-12-01 Dic株式会社 Aqueous urethane resin composition and articles

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6270431A (en) * 1985-09-25 1987-03-31 Unitika Ltd Production of polyamino acid urethane resin film
JPH0753764A (en) 1993-08-17 1995-02-28 Asahi Chem Ind Co Ltd Production of porous polyurethaneurea film for medical use
JP3441298B2 (en) * 1996-06-13 2003-08-25 株式会社クラレ Leather-like sheet having silver surface and method for producing the same
JP2004115982A (en) * 2002-09-30 2004-04-15 Seikoh Chem Co Ltd Method for producing coating cloth
US7311862B2 (en) * 2002-10-28 2007-12-25 Cabot Microelectronics Corporation Method for manufacturing microporous CMP materials having controlled pore size
EP2559729A4 (en) * 2010-04-16 2015-03-25 Asahi Glass Co Ltd Fluorine-containing copolymer composition and production method for same
US10385505B2 (en) 2013-09-06 2019-08-20 Dic Corporation Urethane resin composition, leather-like sheet, and method for producing the leather-like sheet

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0636474A1 (en) * 1993-07-28 1995-02-01 Shell Internationale Researchmaatschappij B.V. A process for preparing laminates, and laminates so prepared
EP0943310A1 (en) * 1998-03-09 1999-09-22 L'oreal Film-forming composition comprising aa aqueous polyurethane dispersion and a plasticizer
JP2005238597A (en) * 2004-02-25 2005-09-08 Terumo Corp Sheetlike porous body and its manufacturing method
CN101945949A (en) * 2008-02-25 2011-01-12 Dic株式会社 Manufacture method, porous polyurethane object and the water vapour permeability film of the solvable type polyurethane resin combination of alcohol
JP4586944B1 (en) * 2009-05-25 2010-11-24 Ｄｉｃ株式会社 Porous body manufacturing method and porous body, laminate and leather-like sheet obtained thereby
JP2011073112A (en) * 2009-09-30 2011-04-14 Fujibo Holdings Inc Polishing pad and method of manufacturing polishing pad
WO2016190080A1 (en) * 2015-05-25 2016-12-01 Dic株式会社 Aqueous urethane resin composition and articles

Also Published As

Publication number Publication date
CN110892012A (en) 2020-03-17
US20210130566A1 (en) 2021-05-06
EP3663343A4 (en) 2021-04-28
EP3663343A1 (en) 2020-06-10
TW201910405A (en) 2019-03-16
WO2019026446A1 (en) 2019-02-07
TWI749248B (en) 2021-12-11
US11111353B2 (en) 2021-09-07

Similar Documents

Publication Publication Date Title
CN110892012B (en) Method for producing porous body
KR101800650B1 (en) Polishing pad
CN109937219B (en) Aqueous polyurethane resin composition and synthetic leather
JP4586944B1 (en) Porous body manufacturing method and porous body, laminate and leather-like sheet obtained thereby
CN112703287B (en) Synthetic leather
CN112673130B (en) Synthetic leather
CN112236555B (en) Synthetic leather
CN113167023A (en) Urethane resin composition, coating film, and synthetic leather
CN114539500A (en) Wet film-forming material
CN111349213B (en) Polyurethane resin composition and polishing pad
KR101492728B1 (en) polyurethane resin composition for artificial leather impregnation
CN116355178A (en) Wet film forming material
JP6460298B1 (en) Method for producing porous body
CN112236554B (en) Synthetic leather
CN112029404B (en) Method for producing porous body
JPWO2020116304A1 (en) Synthetic leather
CN113265138A (en) Urethane resin composition and method for producing porous body
JP7331453B2 (en) Method for manufacturing porous body
TWI837099B (en) synthetic leather
JP2023044910A (en) Urethane resin composition and method for producing porous body
TW202041560A (en) Urethane resin composition and synthetic leather

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant